UGPA4023 Gas Process Engineering

Topic 3e (PROCESS CLASSIFICATION)

Acid Gas Removal

Gas Process Engineering - Topic 3e (Process Classification) – Acid Gas Removal 1

 Purpose
• To reduce ‘acid gas’: O2 & H2S along with
other sulfur species, to sufficiently low levels
to meet contractual specifications or permit
additional processing in the plant without
corrosion and plugging problems.

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 Problem
• H2S is highly toxic, and in the presence of
water it forms a weak, corrosive acid. The
threshold limit value (TLV) for prolonged
exposure is 10 ppmv and at concentrations
greater than 1,000 ppmv, death occurs in
minutes.
• H2S can form other sulfur species carbon
disulfide (CS2), mercaptans (RSH), and
sulfides (RSR), in addition to elemental sulfur.
• If CO2 is present, can form carbonyl sulfide
(COS).
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 Problem
• For gas to be processed as NGL recovery or
nitrogen rejection in a cryogenic
turboexpander process, CO2 may have to be
removed to prevent formation of solids.

• If the gas is being fed to an LNG liquefaction

facility, then the maximum CO2 level is about
50 ppmv.

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 Acid Gas Disposal
• If CO2 quantities are large, it is sometimes used
as an injection fluid in EOR (enhanced oil
recovery) projects.
• For H2S:
• Incineration and venting, if environmental
regulations regarding sulfur dioxide emissions can
be satisfied
• Reaction with H2S scavengers, such as iron sponge
• Conversion to elemental sulfur by use of the Claus
or similar process
• Disposal by injection into a suitable underground
formation
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 Acid Gas Removal Process

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 Factors for Process Selection
• The type and concentration of impurities and
hydrocarbon composition of the sour gas.
• The temperature and pressure at which the sour gas is
available.
• The specifications of the outlet gas, the selectivity
required for the acid gas removal
• The volume of gas to be processed.
• The capital, operating, and royalty costs for the
process.
• The environmental constraints, including air pollution
regulations and disposal of byproducts considered
hazardous chemicals.
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Acid Gas Removal ProcessSelection

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Acid Gas Removal ProcessSelection

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Acid Gas Removal ProcessSelection

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Acid Gas Removal ProcessSelection

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Acid Gas Removal ProcessSelection

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 Solvent Absorption Process
2 major cost factors:
•Key Factors for Plant Operators:
-solvent circulation rate (affects both
equipment size and operating costs)
-energy requirement to regenerate
solvent.

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Solvent Absorption Process

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 Solvent Absorption Process
1. Amines
o Mostly use aqueous Alkanolamines.
o Advantages:
 Complete removal of acid gases at high flow rates.
 Treatment sour gas with lowest partial pressure of H2S
& CO2.
 Amine solution tailored for sour gas composition.
o Limitations:
 High CAPEX
 Higher OPEX
 Larger Size & Weight
 BTEX and Salt Removal
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Solvent Absorption Process

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 Solvent Absorption Process
Amines remove H2S and CO2 in a two
step process:
1. The gas dissolves in the liquid
(amines).
2. The dissolved gas, which is a weak
acid, reacts with the weakly basic
amines.

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 Solvent Absorption Process
Types of amines:

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 Solvent Absorption Process
Monoethanolamine (MEA):
1. most basic, most reactive for acid gas
removal.
2. advantage: high solution capacity at
moderate concentrations, and it is
generally used for gas streams with
moderate levels of CO2 and H2S when
complete removal of both impurities is
required.

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 Solvent Absorption Process
Monoethanolamine (MEA):
3. Disadvantages:
• high vaporization losses
• formation of irreversible reaction products
with COS and CS2
• high energy requirements for regeneration
• inability to selectively remove H2S in the
presence of CO2
• higher corrosion rates
• formation of corrosive thiosulfates when
reacted with oxygen
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 Solvent Absorption Process
• “heat stable salts” form in all alkanol amine
solutions, primarily from reaction with CO2.
• Oxygen enhances the formation of the salts.
• high concentrations of salts can carry over to
the contactor and cause foaming, which
degrades contactor efficiency.
• “reclaimers” are installed in-line for
intermittently removing these salts along
with the irreversible reaction products
formed from COS and CS2
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 Solvent Absorption Process
Diglycolamine (DGA):
Low vapor pressure allows DGA to be used in
relatively high concentrations (50 to 70%),
which results in lower circulation rates.

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 Solvent Absorption Process
Diethanolamine (DEA):
• less basic and reactive than MEA.
• lower evaporation losses
• can operate at higher acid gas loadings
• lower energy requirement for reactivation
• concentration ranges for DEA are 30 to 50
wt% and are primarily limited by corrosion.
• forms regenerable compounds with COS
and CS2 and, thus, can be used for their
partial removal without significant solution
loss.
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 Solvent Absorption Process
Diethanolamine (DEA):
Disadvantages:
• irreversible side reactions with CO2 and
forming corrosive degradation products (not
suitable for high CO2 gas inlet)

Removal of these degradation products along

with the heat stable salts must be done by use
of either vacuum distillation or ion exchange.

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 Solvent Absorption Process
Methyldiethanolamine (MDEA):
• selectively removes H2S to pipeline
specifications while “slipping” some of the
CO2 (by reducing the contact time because
H2S hydrolysis is much faster than that for
CO2)
• low vapor pressure, can be used at
concentrations up to 60 wt% without
significant vaporization losses.

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 Solvent Absorption Process
Mixed Amines:
• Tailor-made: selectivity of MDEA can be
reduced by addition of MEA, DEA, or
proprietary additives.
• to meet the desired amount of CO2 slippage
and still have lower energy requirements.

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 Solvent Absorption Process
Heats of Reaction:
• important, because the heat liberated in the
reaction must be added back in the
regeneration step.

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 Amine treating by use of MEA

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 Solvent Absorption Process
Amine Reclaiming (For MEA and DGA):
• Amines react with CO2 and contaminants,
including oxygen, to form organic acids,
acids then react with the basic amine to form
heat stable salts (HSS).
• Reclaimer is semicontinuous distillation
process, filled with lean amine, and a strong
base, such as sodium carbonate or sodium
hydroxide, to neutralize the heat stable salts.

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 Alkali Salt

Use hot potassium carbonate process for

removing CO2 and H2S:

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Hot potassium carbonate process

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Gas Process Engineering - Topic 3e (Process Classification) – Acid Gas Removal 1
 Physical Absorption
• no chemical reaction occurs.
• example: Selexol or Rectisol.
• advantages and disadvantages:
• most efficient when the partial pressures of the acid
gases are relatively high
• most efficient when low concentrations of heavier
hydrocarbons in the inlet
• selective removal of sulfur compounds, allows CO2
to be slipped
• energy requirements for regeneration of the solvent
are lower (at near-ambient temperature)
• Partial dehydration occurs (whereas amine
processes produce a water saturated product
stream) Gas Process Engineering - Topic 3e (Process Classification) – Acid Gas Removal 3
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 Selexol
• is a polyethylene glycol

• can reduce H2S

to 4 ppmv
• reduce CO2 to
levels below
50 ppmv

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 Selexol

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 Selexol

Solubility of various gases in Selexol solvent at 70°F (21°C)

as a function of partial pressure.
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 Selexol

Selexol gas treating facility.

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 Selexol

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 Absorption
• synthetic zeolites / molecular sieve (molecular
sieve can reduce H2S levels to 6 mg/m3).
• can work when inlet acid gas at low partial
pressures
• Limitation:
• water displaces acid gases on the adsorbent
bed.
• equire regeneration of the bed at 600°F
(315°C) for extended time with the potential
for COS formation if 4A is used.
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 Membrane
in natural gas processing for:
• dehydration
• fuel-gas conditioning
• bulk CO2 removal √√
• solution-diffusion type 0.1 to 0.5 μm
cellulose acetate
• about 80% of gas separation membranes
are formed into hollow fiber modules

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Membrane

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 Membrane
Operating condition:
• Flow pattern

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 Membrane
Operating condition:
• Flow rate
• Operating temperature
• Operating pressure
• Feed gas pre-treatment
• Liquids.
• High-molar-mass hydrocarbons (C15+)
such as compressor lube oils.
• Particulates.
• Corrosion inhibitors and well additives.

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 Membrane
Pre-treatment method:

Limitation:
1. adsorbent bed is the only unit that removes
heavy hydrocarbons
2. ( )
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 Membrane
Advantages:
• Low capital investment when compared with
solvent systems
• Ease of operation: process can run unattended
• Ease of installation: Units are normally skid
mounted
• Simplicity: No moving parts for single-stage units
• High turndown ratio: The modular nature of the
system means very high turndown ratios can be
achieved
• High reliability and on-stream time
• No chemicals needed
• Good weight and space efficiency
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 Membrane
Disadvantages:
• Economy of scale: Because of their modular
nature, they offer little economy of scale
• Clean feed: Pretreatment of the feed to the
membrane to remove particulates and liquids is
generally required
• Gas compression: Because pressure difference is
the driving force for membrane separation,
considerable recompression may be required for
either or both the residue and permeate streams

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 Membrane
Disadvantages (for natural gas systems):
• Generally higher hydrocarbon losses than solvent
systems
• H2S removal: H2S and CO2 permeation rates are
roughly the same, so H2S specifications may be
difficult to meet
• Bulk removal: Best for bulk removal of acid gases;
membranes alone cannot be used to meet ppmv
specifications

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Nonregenerable Hydrogen Sulfide
Scavengers
• Applicable when the quantity of sulfur to be
recovered is small (<= 180 kg/d)
• Most widely used: iron oxides, especially iron
sponge
• Also, liquid oxidation−reduction (redox) processes
use iron as an oxidizing agent in solution

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Nonregenerable Hydrogen Sulfide
Scavengers
four basic steps:
1. Removal of H2S from the gas by absorption into a
caustic solution
2. Oxidation of the HS− ion to elemental sulfur via the
oxidizing agent
3. Separation and removal of sulfur from the solution
4. Regeneration (i.e., oxidation) of the oxidizing agent
by use of air

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Safety and Environmental Considerations

• Amines
• Physical Absorption
• Adsorption
• Scavenger

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